CN85104036A

CN85104036A - Directly produce the production method of sodium stannate from the tin concentrate

Info

Publication number: CN85104036A
Application number: CN198585104036A
Authority: CN
Inventors: 刘希澄; 郑文裕
Original assignee: GUANGDONG POLYTECHNICAL COLLEGE
Current assignee: GUANGDONG POLYTECHNICAL COLLEGE
Priority date: 1985-05-23
Filing date: 1985-05-23
Publication date: 1986-11-19
Also published as: CN85104036B

Abstract

The invention belongs to the production method of chemical industry metallurgical production compound, is directly to change into thick sodium stannate from the tin concentrate; And solved leaching, the purification of thick sodium stannate, the condensing crystal of refined liquid, and technical problem such as product oven dry.Can obtain to meet the first grade of Guangzhou Q/HGI-58-84 company standard and the product that foreign export requires.The direct yield of Sn reaches 80.15, and total yield is 95.88%.

The invention solves the contrary processing problems of classical approach with refined tin system sodium stannate.Save energy and material, Sn rate of recovery height, cost are low, remarkable in economical benefits, flow process is short, and equipment is simple, and mother liquor can return use, and is free from environmental pollution.

Description

Directly produce the production method of sodium stannate from the tin concentrate

The invention belongs to the production method of the production method of chemical industry metallurgical production compound, particularly sodium stannate.

At present, producing sodium stannate both at home and abroad all is as raw material with refined tin.With refined tin as the raw material production pink salt, be a kind of contrary processing, it must be with the tin concentrate by processes such as retailoring, the pyrorefining of crude metal tin and electrorefinings, and then under the oxygenant existence condition, be converted into thick sodium stannate with alkali reaction with the gained refined tin, just obtain sodium stannate by technologies such as leaching, removal of impurities, condensing crystals again.This production technique is owing to exist contrary process, the make energy, chemical materials waste, simultaneously, when making the raw material production sodium stannate with refined tin, because the fusing point of tin is low, proportion is bigger than molten caustic soda again, react at the beginning, tin promptly melts and is sunken to the bottom of a pan, is unfavorable for reacting carrying out, make the transformation efficiency of tin low, generally have only 40～70%.Technological process that is proposed in " nonferrous smelting " the 8th phase nineteen eighty-three " is produced sodium stannate " from the low-grade scruff literary composition and existing processing method are relatively, technological process shortens to some extent, but its material composition is based on tin chloride, does not have a ubiquity, still needs secondary crystal on the technology.

The present invention is directed to the original production method exists against the low problem of transformation efficiency of processing and tin, purpose is to seek a kind of novel method of directly producing sodium stannate with the tin concentrate, thereby avoided the contrary course of processing, save energy and chemical raw material, make the transformation efficiency height of tin simultaneously, technology, equipment are simple, reduce product cost.

Production method of the present invention mainly is directly the tin concentrate to be fused with sodium hydroxide under 450～500 ℃ temperature, and its chemical equation is:

Thick sodium stannate is produced in fusion, passes through operations such as leaching, purification, removal of impurities condensing crystal, dewatered drying again, obtains sodium stannate.

The ratio of components of tin concentrate and sodium hydroxide during fusion=1: 1.5～2, fusion temperature are 450～500 ℃, keep 500 ℃ about 1 hour, 2～3 hours total fusion time.Under agitated conditions, carry out.At the fusion initial stage, concentrate and fused EaOH mix, and are scattered paste shape, and help reaction and carry out, so the transformation efficiency height of tin.When fusion finishes, form the sticky shape product of lark, take out cooling, the cooling back is broken block into about 2 * 2 centimeters sizes, in order to leaching.During leaching, the sodium stannate in the fused material dissolves in the aqueous solution, and it is separated with most of impurity with slag, purifies impurity such as the arsenic removed in the leach liquor, antimony, lead, silicon then, and available air or hydrogen peroxide become high price iron with ferrous oxidation, make arsenic be the ferric arsenate precipitation; Ageing (leaving standstill) leach liquor 3～5 days makes silicate cohesion desiliconization; And be cooled to 3～7 ℃, make sodium arseniate with Na ₃AsO ₄12H ₂O separates out; The tinfoil paper displacement of cleaning with 1: 1 hydrochloric acid removes antimony again, and subsidiary deleading.

Leach liquor after purifying is concentrated, make Na between control ratio focuses on 1.27～1.3 ₂SnO ₃3H ₂The O crystallization is separated out, and filters and takes out crystallization, and with 15～20%NaOH solution washing crystallized product, oven dry promptly gets product under 70～75 ℃ of temperature.

With explained hereafter sodium stannate of the present invention, can economize the whole process of detin concentrate refined tin, thereby a large amount of energy and industrial chemicals have been saved, and when adding sodium hydroxide directly fuses in the tin concentrate, the leaching yield of tin can be up to about 98%, and the direct yield of whole technology tin reaches 80%, and total yield reaches 95%, and processing unit of the present invention is simple, and cost of material is cheap, be easy to get.Industrial scale is changeable, the economical effectiveness height.The non-environmental-pollution problem.

One embodiment of the present of invention: its technical process such as Fig. 1.

Raw materials used is the tin ore that the purchase ore deposit people of Guangning County mining and metallurgy industrial are produced, and it is higher to contain arsenic, its analysis of chemical elements result such as table 1.

The main process of production technique

1. fuse ratio of components=1: 1.5～2 of tin concentrate and sodium hydroxide, at this moment, the tin in the tin concentrate can well change into sodium stannate.The leaching yield of continuous back tin can be up to about 98%, and the temperature during fusion is 450～500 ℃, reacts anxious strong in the time of 400～450 ℃, need add strong mixing, in order to avoid rafting emits pot to overflow.In 500 ℃ of insulations about 1 hour, about 2～3 hours of total fusion time.

Table 1 tin concentrate composition

Element

Sn

As

Pb

Sb

S

Fe

Mn

Content %

65.19

1.20

0.013

0.11

1.40

2.62

0.108

Element

Ni

SiO ₂

WO ₃

Mo

Ta ₂O ₃

Nb ₂O ₃

Cu

Content %

＜0.05

4.21

1.17

＜0.005

0.18

0.12

0.11

With the heating of well formula resistance furnace, temperature is controlled with DRZ-4 type temperature regulator during fusion.

Fusion available wrought iron of pot or cast iron manufacturing, impure higher in several leading the rafting in the time of cylinder iron, must strengthen purifying, then there is not this phenomenon during with wrought iron pan.

2. leach the sodium stannate that makes in the fusion material and change the aqueous solution over to, it is separated with slag and most of impurity.Leach operation and at room temperature carry out, help the sodium stannate dissolving like this, and sodium antimonate is stayed in the slag basically.

Leaching can be at the porcelain enamel barrel with electronic agitator, carries out in the leaching vat of iron (or stainless steel) system, adds leaching vat by liquid-solid ratio=4～5 water requirement during leaching, progressively adds the fusion material under agitated conditions, according to the reinforced speed of temperature rising situation control.Leaching stirring velocity can be between 150～300 rev/min, and extraction time 1～1.5 hour purifies leach liquor again.

3. purify impurity such as the arsenic remove in the leach liquor, antimony, lead, silicon, can this be the key that obtain qualified product.Leach liquor is adopted purifying method of the present invention,, just can obtain meeting the qualified product of Guangzhou Q/HCI-58-84 company standard through the once concentration crystallization.Also can produce the product that meets the foreign export requirement.Each constituent content is as shown in table 2 before and after the purification of leaching liquor.

Purification and impurity removal equipment, available porcelain enamel barrel or stainless steel tank.

4. the solution behind the condensing crystal purification and impurity removal carries out in the steam jacket of belt stirrer or electrically heated stainless steel tank, is concentrated into 1/2～1/3 of original volume, and control ratio focuses between 1.27～1.3, makes Na ₂SnO ₃3H ₂The O crystallization is separated out.

Table 2

5. the Na that goes out of dewatered drying crystallization ₂SnO ₃3H ₂O filters with the stainless steel whizzer, and also vacuum available suction strainer equipment filters.With 15～20%NaOH solution washing crystallized product of 70～75 ℃, the sodium stannate behind the filtration washing is contained in enamel tray or Stainless Steel Disc after filtering, and delivers to the kiln oven dry.The kiln used vapour, infrared or resistive heating.Temperature is controlled at 100～140 ℃ during oven dry, 2～4 centimeters of bed thickness, drying time 6～10 hours.

After the sodium stannate product drying, sampling analysis, its result is as shown in table 3.

Table 3

6. mother liquor is handled the mother liquor that condensing crystal filters out and is merged with washing lotion, and natural cooling crystallization is separated out sodium arseniate, the mother liquor after the sodium arseniate filtering separation, can concentrate and return fusion workshop section and use; Also can directly deliver to fusion workshop section and concentrate and use removing mother liquor behind the sodium arseniate.The sodium arseniate that crystallization goes out can be made byproduct and sell, and makes finings to glasswork and uses.

7. metal is accounted and technico-economical comparison calculates to handle 1 kilogram of tin concentrate, its raw materials consumption, and the sodium stannate output capacity, the rate of recovery of Sn etc. is listed in table 4.

As can be seen from Table 4, the direct yield of Sn is 80.15%; The total yield of Sn is 95.88%; The leaching yield of Sn is 96.32%, but 1.34 kilograms of per kilogram concentrate output sodium stannates; But 2.03 kilograms of per kilogram amount of metal concentrate output sodium stannates; 0.597 kilogram in per kilogram sodium stannate consumption alkali; 0.8 kilogram in per kilogram concentrate consumption alkali.

Table 4 raw materials consumption and sodium stannate output capacity

Claims

1, a kind of method of producing sodium stannate comprises operations such as fusion, leaching, purification, condensing crystal, dewatered drying, it is characterized in that with the tin concentrate be raw material, with the sodium hydroxide fusion, directly leaches under 450～500 ℃ temperature.

2, according to the said method of claim 1, it is characterized in that leach liquor through purifying, primary crystallization is produced sodium stannate.

3, according to the said method of claim 1, it is characterized in that scavenging agent is a thick sodium stannate when leaching, with air or hydrogen peroxide ferrous oxidation is become high price iron, make arsenic be the ferric arsenate precipitation, carry out preliminary arsenic removal.

4, according to the said method of claim 1, it is characterized in that purifying method is thick sodium stannate leach liquor ageing (leaving standstill) 3～5 days, make silicate cohesion desiliconization, and make 3～7 ℃ of leach liquor coolings, make sodium arseniate with Na, AsO ₄12H ₂O separates out, further arsenic removal.

5, according to the said method of claim 1, it is characterized in that thick sodium stannate removes antimony with the tinfoil paper displacement that 1: 1 hydrochloric acid cleaned, and subsidiary deleading.

6,, it is characterized in that 15～20%NaOH solution washing crystalline product (Na with 70～75 ℃ according to the said method of claim 1 ₂SnO ₃3H ₂O).